AZO dyes and compositions comprising such dyes

ABSTRACT

Azo dyes of Formula (1) have utility as dyes for ink-jet printing, where Formula (1) represents:                    
     which comprises any suitable form of the compound: such as salt; stereoisomer, zwitterion, polymorph, complex, isotopic form, combinations thereof in the same species and mixtures thereof; where: n represents from 1 to 5 inclusive; R 1 , R 1B , R 4  and R 4B  each independently comprises at least one of the following substituents, optionally substituted: 
     H, C 1-8 alkyl; C 1-8 ,alkoxy; —NHCOH, C 1-8 alkylcarbonylamino; and —NHCONR 5 R 6    
     where R 5  and R 6  each independently comprises at least one of the 
     following substituents: H, C 1-8 alkyl and aryl; and 
     R 2  and R 3  each independently comprises at least one of the following substituents, optionally substituted: 
     H; C 1-8 alkoxy; -NHC 1-8 alkyleneOH, —SC 1-8 -alkyleneSO 3 H; 
     -NHC 1-8 alkyleneN(C 1-8 alkyl) 2 ;                    
     where X comprises one of the following: —NHC 1-8 alkylene; 
     —NHphenylSO 2 NHC 1-8 alkylene; and a direct link,                    
     where X comprises one of the following: —NHC 1-8 alkylene; 
     —NHphenylSO 2 NHC 1-8 alkylene; and a direct link;                    
     a moiety of Formula ( 2 ) where m and p is each independently from 0 to 5 inclusive, provided that 
     (m+p) is from 1 to 5 inclusive; and 
     R 1A , R 2A , R 4A  and R 4C  each independently comprises at least one of those 
     optionally substituted substituents as defined herein for R 1 , R 2 , R 4  and R 4B    
     respectively; and 
     any other suitable labile or non-labile substituent not mentioned above; where the optional substituents herein comprise: C 1-4 alkyl (optionally substituted with at least one halo)., C 1-4 alkoxy (optionally substituted with at least one halo), carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo.

This invention relates to dyes, to inks and to their use in ink jetprinting (“IJP”). IJP is a non-impact printing technique in whichdroplets of ink are ejected through a fine nozzle onto a substratewithout bringing the nozzle into contact with the substrate.

There are many demanding performance requirements for dyes and inks usedin IJP. For example they desirably provide sharp, non-feathered imageshaving good water-fastness, light-fastness and optical density. The inksare often required to dry quickly when applied to a substrate to preventsmudging, but they should not form a crust over the tip of an ink jetnozzle because this will stop the printer from working. The inks shouldalso be stable to storage over time without decomposing or forming aprecipitate which could block the fine nozzle.

According to the present invention there is provided at least onecompound of Formula (1):

which comprises any suitable form of the compound: such as salt;stereoisomer, zwifterion, polymorph, complex, isotopic form,combinations thereof in the same species and mixtures thereof; where: nrepresents from 1 to 5 inclusive; R¹, R^(1B), R⁴ and R^(4B) eachindependently comprises at least one of the following substituents,optionally substituted:

H, C₁₋₈alkyl; C₁₋₈alkoxy; —NHCOH, C₁₋₈alkylcarbonylamino; and —NHCONR⁵R⁶

where R⁵ and R⁶ each independently comprises at least one of the

following substituents: H, C₁₋₈alkyl and aryl; and

R² and R³ each independently comprises at least one of the followingsubstituents, optionally substituted:

H; C₁₋₈alkoxy; —NHC₁₋₈alkyleneOH, —SC₁₋₈-alkyleneSO×hd 3H;

—NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂;

where X comprises one of the following: —NHC₁₋₈alkylene;

—NHphenyISO₂NHC₁₋₈alkylene; and a direct link,

where X comprises one of the following: —NHC₁₋₈alkylene;

—NHphenyISO₂NHC₁₋₈alkylene; and a direct link;

a moiety of Formula(2)

where m and p is each independently from 0 to 5 inclusive, provided that

(m+p) is from 1 to 5 inclusive; and

R^(1A), R^(2A), R^(4A) and R^(4C) each independently comprises at leastone of those

optionally substituted subsfituents as defined herein for R¹, R², R⁴ andR^(4B) respectively; and

any other suitable labile or non-labile substituent not mentioned above;where the optional substituents herein comprise: C₁₋₄alkyl (optionallysubstituted with at least one halo)., C₁₋₄alkoxy (optionally substitutedwith at least one halo), carboxy, sulpho. hydroxy, amino, mercapto,cyano, nitro and halo with the proviso that one of R² and R³ is a moietyof the Formula (2), then the other R² or R³ is:

a moiety of Formula (2), SC₁₋₈alkyleneSO₃H or —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂; wherein X¹ is NHC₁₋₈alkylene or -NHphenylSO₁₋₈alkylene.

When R² and/or R³ represent a labile atom or group, it is preferably anatom or group which is bound by a chemical bond to the triazine nucleuswhich is displaceable by a hydroxyl group of cellulose under mildlyalkaline aqueous conditions to form a covalent bond between the triazinenucleus and cellulose. Labile atoms and groups that may be representedby R² and/or R³ independently comprise: halo (preferably F and Cl);sulphonic acid groups; thiocyano groups; optionally substitutedquatemary ammonium groups (preferably trialkylammonium groups) and/oroptionally substituted pyridinium groups (preferably 3−and 4−carboxypyridinium groups).

Preferred non-labile groups represented by R² and/or R³ independentlycomprise groups of the formulae —OR⁷, —SR⁸ and/or —NR⁹R¹⁰, morepreferably —OH,—NH₂, —NH (C₁₋₄alkyl) and/or -NH(hydroxyC₂₋₄alkyl). Inthe preceding formulae R⁷, R⁸, R⁹ and/or R¹⁰ are each independentlyselected from the following optionally substituted substituents: H;alkyl (preferably C₁₋₁₀alkyl, especially C₁₋₄alkyl); cycloalkyl; aryl(preferably phenyl); aralkyl [preferably -(CH₂)₁₋₄phenyl, especiallybenzyl]; and R⁹ and R¹⁰ together with the nitrogen atom to which theyare attached form an optionally substituted 5−or 6−membered ring,preferably an optionally substituted morpholine, piperidine orpiperazine ring, more preferably piperazine in which the free ringN-atom is optionally substituted by a C₁₋₄alkyl or hydroxy-C₂₋₄-alkylgroup. When R⁷, R⁸, R⁹ and/or R¹⁰ is substituted, the substituent ispreferably selected from the optional substituents listed above, morepreferably is selected from: hydroxy, methyl, methoxy, sulpho andcarboxy.

Advantageous dyes of Formula (1) are those in which: n is 2; R^(1B) andR^(4B) represent H; R¹ represents H, C₁₋₈alkyl; C₁₋₈alkoxy; -NHCOH,C₁₋₈alkylcarbonylamino; or -NHCONR⁵R⁶; R⁴ represents H, C₁₋₈alkyl orC₁₋₈alkoxy; and R² and R³ each independently represents: H; C₁₋₈alkoxy;—NHC₁₋₈alkyleneOH, —SC₁₋₈-alkyleneSO₃H; —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂,

where X is —NHC₁₋₈alkylene; or a direct link,

where X is —NHC₁₋₈alkylene; or a direct link; and/or a moiety ofFormula(2) where m is 2, p is 0 and R^(4C) represents H; with theproviso that when one of R² and R³ is a moiety of the Formula (2) wherem is 2, p is 0 and R^(4c) represents H, then the other of R² and R³ is

—SC₁₋₈alkyleneSO₃H, —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂ or a moiety of Formula(2) where m is 2, p is 0 and R^(4c) is H, wherein X¹ is NHC₁₋₈alkylene.

Any radical group mentioned above as a substituent refers to amonovalent radical unless otherwise stated. A group which comprises achain of three or more atoms signifies a group in which the chain whollyor in part may be linear, branched and/or form a ring (induding spiroand/or fused rings). The total number of certain atoms is specified forcertain substituents for example C_(1-n)alkyl, signifies an alkyl groupcomprising from 1 to n carbon atoms.. In any of the formulae drawnherein if one or more ring substituents are not indicated as attached toany particular atom on the ring [for example the —CO₂H groups in Formula(1)] the substituent may replace any H attached to an atom in the ringand may be located at any available position on the ring. Hydrocarbonsubstituents or parts of substituents may comprise one or more doubleand/or triple carbon to carbon bonds and the term ‘alkyl’ as used hereinencompasses alkenyl and alkynyl. The term ‘aryl’ as used hereincomprises any suitable hydrocarbon comprising an aromatic moiety. Theterm ‘halo’ as used herein signifies fluoro, chloro, bromo and iodo.

The terms ‘acceptable’ or ‘suitable’ (for example with reference tocomposition ingredients, substituents and/or compounds described herein)will be understood to mean suitable for use in IJP for example byproviding desirable properties to the ink or being compatible with anyinert carriers and/or diluents suitable for formulating such inks. Inrelation to the processes described herein suitable compounds are thosewhich will, in addition, undergo the specified reactions. To beparticularly acceptable for use in IJP compounds of Formula (1) may beAmes negative.

According to a first preferred aspect of the present invention there isprovided at least one mono azo dye of Formula (1), including anysuitable salts and tautomers thereof, in which: n is 2; R^(1B), R⁴ andR^(4B) are all H; R¹ is H, C₁₋₄alkyl, C₁₋₄alkoxy, NHCOH,C₁₋₄alkylcarbonylamino, or -NHCONR⁵R^(6;)

where R⁵ and R⁶ is each independently: H, C₁₋₄alkyl or aryl; and R² andR³ is each independently: —NHC₁₋₄alkyleneOH, —SC₁₋₄alkyleneSO₃H,—NHC₁₋₄alkyleneN(C₁₋₄-alkyl)₂; or

where X is —NHC₁₋₄alkylene or a direct link.

More preferred monoazo dyes of Formula (1) in this first preferredaspect of the invention are those in which: the carboxy groups on thephenyl ring in Formula (1) are meta to the azo group; and R¹ is methylor NHCOCH₃.

According to a second preferred aspect of the present invention there isprovided at least one bisazo dye of Formula (1), including any suitablesalts and tautomers thereof, in which: n is 2; R^(1B) and R^(4B) areboth H; R¹ and R^(1A) is each independently: H, C₁₋₄alkoxy, NHCOH,C₁₋₄alkylcarbonylamino, or NHCONR⁵R^(5;)

where R⁵ and R⁶ is each independently H, C₁₋₄alkyl or aryl; R⁴ andR^(4A) is each independently H, C₁₋₄alkyl or -C₁₋₄alkoxy; R² is a moietyof Formula (2) where m is 2, p is 0 and R^(4C) is H; R^(2A) is H, orC₁₋₄alkoxy; and R³ is: —NHC₁₋₄alkyleneOH, -SC₁₋₄alkyleneSO₃H,-NHC₁₋₄alkyleneN(C₁₋₄-alkyl)₂;

where X is —NHC₁₋₄alkylene or a direct link; provided that when R¹ andR² are methyl, and R^(1A), R⁴ and R^(4A) are all H; R³ is other than—NHC₂H₄OH.

More preferred bisazo dyes of Formula (1) in this second preferredaspect of the invention are those in which: the carboxy groups on thephenyl rings in Formulae (1) and (2) are meta to the azo group; R¹ andR^(1A) is each independently methoxy; -NHCOCH₃., or —NHCONH₃; and R⁴ andR^(4A) is each independently H or methoxy.

According to a third preferred aspect of the present invention there isprovided at least one monoazo dye of Formula (1) (which comprises atleast one piperazinyl substituent), including any suitable salts andtautomers thereof, in which:

n is 2;

R^(1B), R⁴ and R^(4B) are all H;

R¹ is H, C₁₋₄alkyl, C₁₋₄alkoxy, NHCOH, C₁₋₄alkylcarbonylamino, orNHCONR⁵R⁶

where R⁵ and R⁶ is each independently H, C₁₋₄alkyl or aryl; and R² andR³ is each independently: —NHC₁₋₄alkyleneOH, —SC₁₋₄alkyleneSO₃H,—NHC₁₋₄alkyleneN(C₁₋₄-alkyl)₂,

where X is —NHC₁₋₄alkylene or a direct link;

where X is —NHC₁₋₄alkylene or a direct link; provided that at least oneof R² and R³ is

More preferred monoazo dyes of Formula (1) in this third preferredaspect of the invention are those in which: the carboxy groups on thephenyl ring in Formula (1) are meta to the azo group; R¹ is methyl,—NHCOCH₃; —NHCONH₂; or methoxy; and R⁴ is methoxy.

According to a fourth preferred aspect of the present invention there isprovided at least one bisazo dye of Formula (1) (which comprises atleast one piperazinyl substituent), including any suitable salts andtautomers thereof, in which:

n is 2;

R^(1B) and R^(4B) are both H;

R¹ and R^(1A) is each independently: H, C₁₋₄alkyl, C₁₋₄alkoxy; —NHCOH,

C₁₋₄alkylcarbonylamino or NHCONR⁵R⁶

where R⁵ and R⁶ is each independently H, C₁₋₄-alkyl or aryl;

R⁴ and R^(4A) is each independently H, C₁₋₄alkyl or C₁₋₄alkoxy;

R² is a moiety of Formula (2) where m is 2; p is 0 and R^(4C) is H;

R^(2A) is H; and

R³ is

R³ is where X is —NHC₁₋₄alkylene or a direct link.

More preferred bisazo dyes of Formula (1) in this fourth preferredaspect of the invention are those in which: the carboxy groups on thephenyl rings in Formulae (1) and (2) are meta to the azo group; R¹ andR^(1A) is each independently methoxy; —NHCOCH₃ or —NHCONH₂; and R⁴ andR^(4A) is each independently H or methoxy.

Specific compounds of Formula (1) comprise those compounds exemplifiedherein; any suitable salts thereof, preferably the ammonium salts; andany suitable mixtures thereof.

Compounds of Formula (1) may be in the form as shown in the structuresherein (e.g. free acid form) but are preferably in the form of salts.Salts of Formula (1) may be formed from one or more organic andlorinorganic base(s) or acid(s) and compounds of Formula (1) which areacidic and/or basic (for example acid and/or base addition salts). Saltsof Formula (1) comprise all acceptable salts that may be formed frommonovalent and/or multivalent acids and/or bases [for example thoseformed by partial neutralisation of carboxylic acids of Formula (1)where n+m>1]. Salts of Formula (1) also comprise all enantiomeric saltsformed with acceptable chiral acids and/or bases and/or any mixtures ofenantiomers of such salts (for example racemic mixtures). Preferredsalts are alkali metal salts, especially lithium, sodium and potassiumsalts, ammonium and substituted ammonium salts. Especially preferredsalts are salts with ammonia and volatile amines. The dyes may beconverted into a salt using known techniques. For example, an alkalimetal salt of a dye may be converted into a salt with ammonia or anamine by dissolving an alkali metal salt of the dye in water, acidifyingwith a mineral acid and adjusting the pH of the solution to pH 9 to 9.5with ammonia or the amine and removing the alkali metal cations bydialysis. The present invention comprises all acceptable salts ofFormula (1) and any suitable mixtures thereof.

Certain compounds of Formula (1) may exist as one or more stereoisomers,for example, enantiomers, diastereoisomers, geometric isomers,tautomers, conformers and/or suitable combinations thereof possible inthe same species. It is particularly preferred that dyes of Formula (1)comprise all tautomeric forms including those not specificallyillustrated herein. The present invention comprises all acceptablestereoisomers of compounds of Formula (1) and any suitable mixturesthereof.

Certain compounds of Formula (1) may exist as one or more zwitterions,for example, species which comprise two or more centres of ionic charge.The present invention comprises all acceptable zwitterions of Formula(1) and any suitable mixtures thereof.

Certain compounds of Formula (1) may exist as one or more polymorphs,for example, phases, crystalline forms, amorphous forms, solidsolutions, interstitial compounds and/or any suitable mixtures thereof.The present invention includes all acceptable polymorphs of Formula (1)and any suitable mixtures thereof.

Certain compounds of Formula (1) may exist in the form of one or morecomplexes, for example, chelates, solvates, organometallic complexes,and/or complexes with other suitable ligands. Such complexes may beformed between an acceptable substrate in which the compound of Formula(1) and/or the substrate may act as a ligand. The substrate may compriseone or more acceptable solvents to form solvates. The complexes may benon-stoichiometric, for example if the complex is a hydrate it maycomprise a hemihydrate, monohydrate and/or dihydrate. The presentinvention includes all acceptable complexes of Formula (1) and anysuitable mixtures thereof.

Certain compounds of Formula (1) may exist as one or more isotopic formsin which one or more atoms in Formula (1) comprise one or more suitableisotopes. The natural ratios of various isotopes may be altered bysuitable means, for example certain ¹²C atoms in certain compounds ofFormula (1) may be substantially replaced by the less common ¹⁴C and/or¹³C isotopes. Optionally certain isotopic forms of Formula (1) may beradio-active. Certain of the isotopic forms of Formula (1) may be usedas means for selective imaging in imaging devices (for example devicesusing X-rays, positron emission tomography and/or nuclear magneticresonance); and/or as tools to investigate the mode of action ofcompounds of Formula (1) in IJP. The present invention includes allacceptable, isotopic forms of Formula (1) and any suitable mixturesthereof.

The present invention relates to all compounds of Formula (1) even thosewhich may not be directly acceptable for use in IJP because they exhibitundesirable properties. Such compounds may nevertheless have utility inthe field of the present invention for example as intermediates in thepreparation and/or purification of acceptable compounds of Formula (1)and/or as research tools and/or diagnostic aids in relation to IJP.

Compounds of Formula (1) may be prepared the methods described below andby other suitable methods analogous to those described in the art forsimilar azo compounds.

Compounds of Formula (1) in which R³ is other than a moiety of Formula(2) may be prepared by condensing a suitable compound of Formula (3):

with suitable compounds of formulae R²H and R³H.

Compounds of Formula (1) in which R² is a moiety of Formula (2) may beprepared by condensing a suitable compound of Formula (1) in which R³ isCl with a compound of formula R³H in which R³ is other than Cl.

Compounds of Formula (1) in which R² is a moiety of Formula (2) and R³is Cl may be prepared by condensing a suitable compound of Formula (3)preferably in the presence of a base with a suitable compound of Formula(4):

Compounds of Formula (3) may be prepared by condensing with cyanuricchloride, preferably in the presence of a base, a suitable azo compoundof Formula (5):

Compounds of Formula (4) may be prepared by diazotising a suitablearomatic amine of Formula (6):

and coupling the resultant diazonium salt with a suitable compound ofFormula (7):

Compounds of Formula (5) may be prepared diazotising a suitable aromaticamine of Formula (6) to form the corresponding diazonium salt andcoupling with a suitable compound of Formula (8):

The reactions leading to the formation of the compounds of Formula (1)may be performed under conditions that have been described in the art.For example diazotisation is preferably performed at a temperature below6° C., more preferably at a temperature in the range −10° C. to 5° C.Preferably the diazotisation is performed in water, more preferably at apH below 7. Dilute mineral acids, such as HCl or H₂SO₄, are often usedto achieve the desired acidic conditions. The azo dyes may be isolatedby known methods such as spray drying or precipitation followed byfiftration.

An aspect of the present invention comprises an ink comprising at leastone compound of Formula (1) as defined herein and a suitable medium.

According to a further aspect of the present invention there is providedan ink comprising:

(a) from 0.01 to 30 parts of a dye of the Formula (1); and

(b) from 70 to 99.99 parts of a liquid medium or a low melting pointsolid medium;

wherein all parts are by weight and the number of parts of (a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

When the medium is a liquid, preferably component (a) is completelydissolved in component (b). Preferably component (a) has a solubility incomponent (b) at 20° C. of at least 10%. This allows the preparation ofconcentrates which may be used to prepare more dilute inks and reducesthe chance of the dye precipitating if evaporation of the liquid mediumoccurs during storage.

Preferred liquid media include water, a mixture of water and an organicsolvent and an organic solvent free from water.

When the medium comprises a mixture of water and an organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20. Preferably the organic solvent comprising the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. The liquid medium may comprise water and preferably twoor more, more preferably from 2 to 8, water-soluble organic solvents.

Preferred water-miscible organic solvents comprise: C₁₋₆-alkanols,preferably methanol, ethanol, n-propanol, isopropanol, n-butanol,sec-butanol, tert-butanol, n-pentanol, cydopentanol and/or cyclohexanol;linear amides, preferably dimethylformamide and/or dimethylacetamide;ketones andlor ketone-alcohols, preferably acetone, methyl ether ketone,cyclohexanone and/or diacetone alcohol; water-misdble ethers, preferablytetrahydrofuran and/or dioxane; diols, preferably C₂₋₁₂diols (forexample pentane-1,5-diol, ethylene glycol, propylene glycol, butyleneglycol, pentylene glycol, hexylene glycol and/or thiodiglycol) and/oroligo- and/or poly-alkyleneglycols (for example diethylene glycol,triethylene glycol, polyethylene glycol and/or polypropylene glycol);triols, preferably glycerol andlor 1,2,6-hexanetriol; C₁₋₄alkyl ethersof diols, preferably monoC₁₋₄alkyl ethers of C₂₋₁₂diols: {for example2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy] -ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and/or ethyleneglycol monoallylether}; cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam andlor 1,3-dimethylimidazolidone;cyclic esters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide andlor sulpholane; and/or any suitable mixtures thereof.

More preferred water-soluble organic solvents are selected from: cyclicamides (e.g. 2-pyrrolidone, N-methyl-pyrrolidone andN-ethyl-pyrrolidone); diols, (e.g. 1,5-pentane diol, ethyleneglycol,thiodiglycol, diethyleneglycol and triethyleneglycol); C₁₋₄alkyl ethersof diols (e.g. 2-methoxy-2-ethoxy-2-ethoxyethanol); and any suitablemixtures thereof.

A preferred liquid medium comprises:

(a) from 75 to 95 parts water; and

(b) from 25 to 5 parts in total of one or more solvents selected from:diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol; where theparts are by weight and the sum of the parts (a)+(b)=100.

Another preferred liquid medium comprises:

(a) from 60 to 80 parts water,

(b) from 2 to 20 parts diethylene glycol; and

(c) from 0.5 to 20 parts in total of one or more solvents selected from:2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone,caprolactam, pentane-1,5-diol and thiodiglycol; where the parts are byweight and the sum of the parts (a)+(b)+(c)=100.

Examples of further suitable media for inks of the present inventioncomprise a mixture of water and one or more organic solvents aredescribed in U.S. Pat. Nos. 4,963,189, 4,703,113, 4,626,284 and EP0425150-A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., more preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents comprise any of thosedescribed above and mixtures thereof. Preferred water-immisciblesolvents comprise aliphatic hydrocarbons; esters (for example ethylacetate) chlorinated hydrocarbons (for example dichloromethane), ethers(for example diethyl ether) and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably it comprises a polar solvent (for example a C₁₋₄alkanol) toenhance the solubility of the dye in the liquid medium. It is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) and/or analcohol (especially a C₁₋₄alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the ink.

Ink media comprising an organic solvent free from water are particularlyuseful where fast drying times are required and particularly whenprinting onto hydrophobic and non-absorbent substrates, for exampleplastics, metal and glass.

Preferred low melting solid media have a melting point in the range from60° C. to 125° C. Suitable low melting point solids include long chainfatty acids or alcohols, preferably those with C₁₈₋₂₄chains, andsulphonamides. The dye of Formula (1) may be dissolved in the lowmelting point solid or may be finely dispersed in it.

The ink may also contain additional components conventionally used ininks for IJP, for example viscosity and surface tension modifiers,corrosion inhibitors, biocides, kogation reducing additives andsurfactants which may be ionic or non-ionic.

A further aspect of the invention provides a process for printing animage on a substrate comprising applying an ink comprising a dye ofFormula (1) to the substrate by means of an ink jet printer. The inkused in this process is preferably an ink of the present invention asdefined herein.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small orifice onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir by means of aresistor adjacent to the orifice, thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the orifice. Inpiezoelectric ink jet printers the oscillation of a small crystal causesejection of the ink from the orifice.

The substrate is preferably paper, plastic, a textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper. Preferred papers are plain or treated paperswhich may have an acid, alkaline or neutral character.

A further aspect of the present invention provides a paper, an overheadprojector slide or a textile material printed with an ink and/or a dyeas defined herein and/or by means of a process as defined herein.

When the substrate is a textile material the ink according to theinvention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer;and

ii) heating the printed textile material at a temperature of from 50° C.to 250° C.

Preferred textile materials are natural, synthetic and semi-syntheticmaterials. Examples of preferred natural textile materials include wool,silk, hair and cellulosic materials, particularly cotton, jute, hemp,flax and linen. Examples of preferred synthetic and semi-syntheticmaterials include polyamides, polyesters, polyacrylonitriles andpolyurethanes.

Preferably the textile material has been treated with an aqueouspre-treatment composition comprising a thickening agent and optionally awater-soluble base and a hydrotropic agent and dried prior to step i)above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.Particularly preferred pre-treatment compositions are described morefully in EP 0534660-A.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

5-Aminoisophthalic acid (36.2 g) was dissolved in water (1 dm₃) adjustedto pH 8.0 with NaOH solution and sodium nitrite (13.8 g) was added. Theresulting solution was poured onto a mixture of ice, water and HCI (50cm³) over 10 minutes at a temperature of between 0 to 10° C. and stirredfor 2 hours also at 0 to 10° C. Excess nitrite was removed withsulphamic acid.

m-Toluidine (21.4 g) was stirred in water (500 cm³) and concentrated HCI(25 cm³) was added. This solution was poured into the above prepareddiazo solution and the pH of the resultant solution was adjusted to 4with sodium acetate. The reaction mixture was stirred at roomtemperature for 16 hours and then filtered to collect a solid which wasdried in an oven at 65° C. under reduced pressure to give 65.6 g ofproduct.

ii) The compound (8.5 g) from i) above was added to water (300 cm³) atpH 8. The resulting solution was added slowly to a stirred suspension ofcyanuric chloride (4.6 g) in acetone (50 cm³). The mixture was thenpoured onto a mixture of ice and water (100 g) at 0 to10° C. and at pH 6to 7 and stirred for 2 hours also at 0 tolO° C and pH 6 to 7 until thinlayer chromatography (TLC) showed that the reaction was complete.

3-Mercapto-1-propane sulphonic acid (4.8 g) was dissolved in water (100cm³) and added to the mixture which was then stirred at pH 8.0 and roomtemperature for 16 hours.

A further portion of 3-mercapto-1-propane sulphonic acid (13.5 g) inwater (100 cm³) was added to the mixture which was warmed to 50° C. andkept at pH 8 to 9 for 6 hours and then was cooled to room temperature.

Sodium chloride solution (20% w/v) was added to the mixture which wasslowly acidified to pH 4 with concentrated HCl. A dry solid wascollected by filtration under reduced pressure. The solid product addedto water (400 cm³) to form a slurry the pH of which was adjusted to 9with ammonia solution. The slurry was poured onto concentrated HCl (30cm³). A solid was collected from the slurry by filtration and thendissolved in ammonia. The pH of the solution was adjusted to 4 withconcentrated HCl and the precipitated solid collected by filtration togive the title compound (8.5 g).

EXAMPLE 2

5-Aminoisophthalic acid (36.2 g) was dissolved with stirring in water(400 cm³) the pH of which was adjusted to 8 to 9 with caustic sodasolution. Sodium nitrite (15 g) was added and the mixture was stirred todissolve. Concentrated HCI (100 cm³) in ice was added at 0 to 10° C. andthe mixture was stirred for 2 hours also at 0 to 10° C. to diazotise.Excess nitrite was removed with sulphamic acid.

m-Aminoacetanilide (55.5g) was stirred in water (400 cm³) at pH 7 andadded to the diazo suspension at 0 to 10° C. and stirred at a pH of 4 to5 with sodium acetate. The mixture was allowed to warm to roomtemperature over 16 hours. A solid was collected from the reactionmixture by filtration and then dried in an oven at 60° C. for 16 hoursto give 111.1 g of product.

ii) The compound (12.7 g) from i) above was added to water (460 cm³) atpH 8. The resulting solution was added slowly to a stirred suspension ofcyanuric chloride (6.9 g) in acetone (75 cm³) and poured into ice (150g) and stirred at 0 to10° C. and pH 6 to 7 for 2 hours until TLC showedthe reaction was complete.

Morpholine (3.6g) was added to the mixture which was then stirred at pH8 to 9 and room temperature for 16 hours.

3-Mercapto-1-propane sulphonic acid (20.2 g) was added to the mixturewhich was stirred at 40 to 45° C. at pH 8 to 9 for 5 hours and then wascooled to room temperature.

The mixture was acidified to pH 4 with concentrated HCl and a dry solidwas collected by filtration under reduced pressure. The solid obtainedwas restirred in water (800 cm³) the pH of which was adjusted to 9 withammonia solution. The mixture was poured onto concentrated HCl (50 cm³)and stirring for 10 minutes and a solid was collected from the mixtureby filtration under reduced pressure and dried in an oven at 60° C. for16 hours to give the title compound (14.6 g).

EXAMPLE 3

The compound (8.5 g) from Example 2 i) above was added to water (300cm³) at pH 8. The resulting solution was added slowly to a stirredsuspension of cyanuric chloride (4.6 g) in acetone (50 cm³) and pouredonto a mixture of ice and water (100 g) at 0 to 10° C. and at pH 6 to 7then stirred for 2 hours at 0 to 10° C. and pH 6 to 7 until TLC showedthe reaction was complete.

3-Mercapto-1-propane sulphonic acid (4.8 g) was dissolved in water (100cm³) and added to the mixture and stirred for 16 hours at pH 8 to 9 androom temperature.

A further portion of 3-mercapto-1-propane sulphonic acid (13.5 g) inwater (100 cm³) was added and the mixture was warmed to 50° C., kept atpH 8 to 9 for 6 hours and then was cooled to room temperature.

Sodium chloride solution (20% w/v) was added to the mixture which wasslowly acidified to pH 4 with concentrated HCl. A solid was collected byfiltration under reduced pressure. The resultant solid was restirred inwater (400 cm³) adjusted to a pH of 9 with ammonia solution. The pH ofthe solution was then adjusted to 4 with concentrated hydrochloric acidand the precipitated solid collected by filtration to give the titlecompound (8.7 g).

EXAMPLE 4

5-Aminoisophthalic acid (36.2 g) was dissolved with stirring in water(400 cm³) the pH of which was adjusted to 8 to 9 with caustic sodasolution. Sodium nitrite (15 g) was added and stirred to dissolve.Concentrated HCI (100 cm³) in ice was added at 0 to 10° C. and themixture was stirred for 2 hours also at 0 to 10° C. to diazotise. Theexcess sodium nitrite was removed with sulphamic acid.

m-Ureidoaniline (57.2 g) was stirred in water (400 cm³) at pH 7 andadded at 0 to10° C. with stirring to the diazo suspension the pH ofwhich was adjusted to 4 to 5 with sodium acetate. The mixture wasallowed to warm to room temperature over 16 hours. A solid was collectedby filtration under reduced pressure and dried in an oven at 60° C. for16 hours to give 153.3 g of product.

ii) The compound (8.6 g) from i) above was added to water (300cm³) at pH8. The resulting solution added slowly to a stirred suspension ofcyanuric chloride (4.6 g) in acetone (50 cm³) and poured on to a mixtureof ice and water (100 g) at 0 to 10° C. and at pH 6 to7 and stirred for2 hours also at 0 to 10° C. and pH 6 to 7 until TLC showed the reactionwas complete.

3-Mercapto-1-propane sulphonic acid (4.8 g) was dissolved in water (100cm³) and added to the mixture which was then stirred for 16 hours at pHof 8 to 9 and room temperature.

A further portion of 3-mercapto-1-propane sulphonic acid (13.5 g) inwater (100 cm³) was added and the mixture was warmed to 50° C., kept atpH 8 to 9 for 6 hours and then was cooled to room temperature.

A solid was isolated as described in the last paragraph of Example 3above, to give the title compound (6.3 g).

EXAMPLE 5

5-Aminoisophthalic acid (27.1 g) was dissolved with stirring in water(200 cm³) at pH 8 to 9. Sodium nitrite solution (75 cm^(3,) 2N) wasadded and the mixture was poured slowly onto a stirred solution ofhydrochloric acid (75 cm³) in ice and the diazotisation was allowed toproceed for 2 hours at 0 to 10° C. Excess nitrate was removed withsulphamic acid.

2,5-Dimethoxyaniline (23 g) was dissolved with stirring in warmedethanol (300 m³) and the solution was cooled and added slowly to diazosolution prepared above. The mixture was stirred for 16 hours. A solidwas collected by filtration under reduced pressure and was dried in anoven at 60° C. for 16 hours.

ii) The compound (14.7 g) from i) above was added to water (250 cm³) atpH 8-9. The resulting suspension was added to a suspension of cyanuricchloride (4.6 g) in acetone (50 cm³) and poured onto a mixture of iceand water (100 cm³) at 0 to 10° C. A few drops of calsolene oil wereadded to the mixture and the pH was adjusted to 8 to 9.

3-Mercapto-1-propane sulphonic acid (4.8 g) was added and the mixturewas stirred for 16 hours at room temperature and a pH of 8 to 9.

A further portion of 3-mercapto-1-propane sulphonic acid (13.5 g) wasadded and the mixture was stirred at pH 8 to 9 and 50° C. for 6 hoursand then was cooled to room temperature.

Sodium chloride solution (20% w/v) was added and the reaction mixturewas acidified to pH 3 with concentrated HCI and strirred for 16 hours atroom temperature. A solid was collected by filtration under reducedpressure. The solid was restirred in water (400 cm³) at pH 9 withammonia solution and poured onto concentrated HCl (30 cm³) and stirredfor 10 minutes. A solid was collected from the mixture by filtrationunder reduced pressure and dried in an oven at 60° C. for 16 hours togive the title compound (11.8 g).

EXAMPLE 6

The compound (14.7 g) prepared as described in Example 5 i) above, wasadded to water (500 cm³) at pH 10. The solution was filtered to remove asmall amount of insoluble material and the filtrate was cooled to 0 to10° C. and then added slowly to a suspension of cyanuric chloride (4.6g) in acetone (50 cm³). The mixture was stirred at 0 to 10° C. and at pH8 to 9 for 1.5 hours. Then a further portion of cyanuric chloride (1 g)in acetone (10 cm³) was added and the mixture was stirred for a further0.5 hours at 0 to 10° C. and pH 8 to 9.

A further portion of the compound (14.7 g) [from Example 5 i) above] inwater (500 cm³) at pH 10 was added and the mixture was stirred at 45 to50° C. and pH 7 to 8 for 16 hours.

3-Mercapto-1-propanesulphonic acid (13.5 g) was added and the mixturewas warmed to 70 to 75° C. for 6 hours and then was cooled to roomtemperature.

The mixture was filtered to remove insoluble material and a solid wasisolated from the filtrate as described in the last paragraph of Example2 above (using 600 cm³ water and 40 cm³ HCl) to give the title compound(17.7 g).

EXAMPLE 7

The procedure of Example 6 was repeated except that at stage iii)morpholine (13.2 g) was used in place of the3-mercapto-1-propanesulphonic acid to give the title compound (15.0 g).

EXAMPLE 8

The compound (7.5 g) prepared as described in Example 1 i) above, wasdissolved with stirring in water (250 cm³) at pH 8. The solution wasadded slowly to a stirred suspension of cyanuric chloride (4.6 g) inacetone (500 cm³). The resultant mixture was poured onto ice (100 g) andstirred at 0 to 10° C. and pH 7 to 8 for 1 hour until TLC showed thereaction was complete.

A further portion of the compound (7.5 g) [from Example 1 i) above] inwater (250 cm³) was added and the mixture was warmed to 45 to 50° C. andpH 7 to 8 for 16 hours.

3-Mercapto-1-propanesulphonic acid (13.5 g) in water (100 cm³) was addedand the mixture was stirred at 45 to 50° C. and pH 8 to 9 for 8 hoursand then was cooled to room temperature.

Sodium chloride solution (20% w/v) was added to the mixture and a solidwas isolated as described in the last paragraph of Example 2 above(using 400 cm³ water and 40 cm³ HCl) to give the title compound (16.4g).

EXAMPLE 9

The compound (12.7 g) prepared as described in Example 2 i) above, wasdissolved with stirring in water (450 cm³) at pH 8. The solution wasfiltered to remove a small amount of insoluble material. The filtratewas added to a stirred suspension of cyanuric chloride (6.9 g) inacetone (100 cm³) and poured onto ice (150 g). The resultant mixture wasstirred at 0 to 10° C. and pH 7 to 8 for 2 hours until TLC showed thereaction was complete.

A further portion of the compound (12.7 g) [from Example 2 i) above] inwater (450 cm³) at pH 8 was added to the mixture which was stirred at pH7 to 8 and 45° C. for 16 hours.

Morpholine (18g) was added and the mixture was stirred at 65 to 75° C.for 60 hours and then was cooled to room temperature.

A solid was isolated from the mixture as described in the last paragraphof Example 2 above, to give the title compound (23.9 g).

EXAMPLE 10

This compound was prepared as described for Example 9 except that2-hydroxyethylamine (12.8 g) was used in place of the morpholine.

EXAMPLE 11

This compound was prepared as described for Example 9 except that3-mercapto-1-propanesulphonic acid (36 g) was used in place of themorpholine.

EXAMPLE 12

The compound (8.5 g) prepared as described in Example 4 i) above, wasdissolved with stirring in water (250 cm³) at pH 8. The solution wasadded slowly to a stirred suspension of cyanuric chloride (4.6 g) inacetone (50 cm³) and poured onto ice (100 g). The resultant mixture wasstirred at 0 to 10° C. and pH 7 to 8 for 1 hour until TLC showed thereaction was complete.

A further portion of the compound (8.5 g) [from Example 4 i) above] inwater (250 cm³) was added and the mixture was warmed to 45 to 50° C. andpH 7 to 8 for 16 hours.

3-Mercapto-1-propanesulphonic acid (13.5 g) in water (100 cm³) was addedand the mixture was stirred at 45 to 50° C. and pH 8 to 9 for 6 hoursand then was cooled to room temperature.

Sodium chloride solution (20% w/v) was added to the mixture and a solidwas isolated as described in the last paragraph of Example 2 above(using 400 cm³ water and 40 cm³ HCl) to give the title compound (11.2g).

EXAMPLE 13

This compound was prepared as described for Example 12 except that2-hydroxyethylamine (4.8 g) was used in place of the3-mercapto-1-propanesulphonic acid.

EXAMPLE 14

5-Aminoisophthalic acid (27.1 g) was dissolved in water (200 cm³) withstirring and the pH was adjusted to 8.0 with NaOH solution, then sodiumnitrite solution (75 ml 2N) was added. The resulting solution was pouredonto a mixture of ice, water and HCI (75 cm³) over 10 minutes at atemperature of between 0 to 10° C. and stirred for 2 hours also at 0 to10° C. Excess nitrite was removed with sulphamic acid.

m-Anisidine (21.4 g) was dissolved with stirring in methanol (200 cm³).This solution was poured into the above prepared diazo solution at atemperature of between 0 to10° C. The mixture was stirred overnightwhilst being warmed slowly to room temperature, and then filtered tocollect a solid. The solid was washed with brine solution and driedunder reduced pressure to give 99.8 g of product.

N-Acetylsulphanilyl chloride (116.5 g) was added to water (600 ml) atroom temperature and the mixture was stirred. 2-Chloroethylaminehydrogen chloride (87 g) was dissolved in water (200 ml) and thissolution was added to the sulphanilyl chloride mixture formed above. ThepH of the mixture was adjusted to pH 7.0 to 7.5 with a 15% solution ofsodium carbonate and the mixture was stirred overnight at roomtemperature. The precipitate formed was collected by filtration underreduced pressure and then wasted with water (2 l) to give a damp paste.

The paste was stirred into 2 N HCl (1 l) at a temperature of 80 to 85°C. for 3 hours, until TLC showed the hydrolysis was complete. Thesolution was cooled to 0 to 10° C. and the pH of the mixture wasadjusted to pH 8.5 by adding solid sodium carbonate, whilst thetemperature of the mixture was kept below 10° C. A solid was collectedby filtration under reduced pressure, washed with water (3 l) and driedin an oven at 70° C. to give 58.5 g of product.

iii) The compound (7.1 g) from i) above was added to water (150 cm³) atpH 8. The resulting solution was added slowly to a stirred suspension ofcyanuric chloride (2.3 g) in acetone (50 cm³). The mixture was thenpoured onto a mixture of ice and water (100 g) at 0 to 10° C. and at pH6 to 7 and stirred for 2 hours also at 0 to10° C. and pH 6 to 7 untilTLC showed that the reaction was complete.

The compound (2.9 g) from ii) above was dissolved in a mixture of water(50 cm³) and methanol (150 cm³). This solution was added at pH 6 to 7and room temperature to the dichloro suspension formed above which wasthen stirred at pH 6 to 7 and 30° C. overnight, until TLC showed thatthe reaction was complete.

Piperazine (20g) was added and the mixture was warmed slowly to 70° C.for 4 hours and then was cooled to room temperature. The mixture wasneutralised to pH 7 with concentrated HCI to form a precipitate whichwas collected by filtration under reduced pressure.

The solid product was added to water (400 cm³) to form a slurry the pHof which was adjusted to 9 with ammonia solution. The slurry was pouredonto concentrated HCI (30 cm³) and stirred for 10 minutes . A solid wascollected from the slurry by filtration under reduced pressure. Theslurrying procedure was repeated twice more to obtain a solid which wasre-stirred in water (400 ml) adjusted to pH 9 with ammonia liquid andpoured onto concentrated HCI (40 cm³) and stirred for 10 minutes. Asolid was collected by filtration under reduced pressure and driedovernight in an oven at 60° C. to give the title compound (8.7 g).

EXAMPLE 15

Sodium bisulphite (84.2 g) was added to water (320 ml) followed by 0.8 Mformaldehyde solution (71.3 g) with stirring. The mixture was warmed to70° C., o-anisidine (98.4 g) was added and then was stirred at 70 to 80°C. for 15 minutes. A solid was collected by filtration under reducedpressure, washed with ethanol (500 ml) and dried overnight in an oven at60° C. to give 156.5 g of product.

5-Aminoisophthalic acid (36.5 g) was dissolved in water (800 cm³) withstirring and the pH was adjusted to 8.0 with NaOH solution, then sodiumnitrite (14 g) was added. The resulting solution was poured onto amixture of concentrated HCl (60 cm³) in ice (100 g) at a temperature ofbetween 0 to10° C. and stirred for 2 hours also at 0 to 10° C. Excessnitrite was removed with a 10% solution of sulphamic acid.

The compound (47.8 g) from i) above was dissolved in water (200 cm³).This solution was poured into the above prepared diazo suspension at atemperature of between 0 to 10° C. The mixture was stirred at pH 6 to 7whilst being warmed slowly to room temperature and then was acidified topH 4.0 with concentrated HCl. The mixture was filtered under reducedpressure to give a paste which was used directly in the next step.

The paste from ii) above was stirred in water (1.5 I) with NaOH pellets(80 g). The mixture was warmed to 75 to 80° C. for 3 hours until TLCshowed that the reaction was complete. The mixture was cooled to roomtemperature, acidified to pH 4.0 with concentrated HCI to form aprecipitate which was collected by filtration under reduced pressure anddried overnight in an oven at 60° C. to give 70.4g of product.

iv) The compound (15.3 g) from iii) above was added to water (300 cm³)at pH 8. The resulting solution was added slowly to a stirred suspensionof cyanuric chloride (9.2 g) in acetone (200 cm³). The mixture was thenpoured onto a mixture of ice and water (200 g) at 0 to 10° C. and at pH7 and stirred for 4 hours also at 0 to10° C. and pH 7 until TLC showedthat the reaction was complete.

A further portion of the compound (15.3 g) from iii) above was dissolvedin water (300 cm³) at pH 8. This solution was added at pH 7 and 30° C.to the dichloro suspension formed above which was then stirred at pH 7and 30° C. overnight.

1-(2-Aminoethyl)piperazine (39.5 g) was added, and the mixture waswarmed to 70±5° C. for 6 hours and then cooled to room temperature.

The mixture was acidified to pH 4.0 with concentrated HCI to form aprecipitate which was collected by filtration under reduced pressure.The solid product was purified as described in the last paragraph ofExample 14 iii) above to give the title compound (20.0 g).

EXAMPLE 16

The compound (14.2 g) prepared as described in Example 14 i) above, wasdissolved in water (300 cm³) the pH of which was adjusted to 8.0 withNaOH. The resulting solution was added over 15 minutes to a solution ofcyanuric chloride (4.6 g) in acetone (50 cm³). The mixture was thenpoured onto ice (100 g) and stirred at 0 to 10° C. for 2 hours at pH 6until TLC showed that the reaction was complete.

1-(2-Aminoethyl)piperazine [4.2g] was added to the reaction mixturewhich was then stirred at room temperature and pH 9 overnight.

A further portion of 1-(2-aminoethyl)piperazine (39.5 g) was added andthe mixture was warmed to 70±5° C. for 6 hours and then cooled to roomtemperature.

The mixture was acidified to pH 6.0 with concentrated HCI to form aprecipitate which was collected by filtration under reduced pressure.The solid product was added to water (400 cm³) to form a slurry the pHof which was adjusted to 9 with ammonia solution. The slurry was pouredonto concentrated HCI (20 cm³) and stirred for 10 minutes. A solid wascollected from the slurry by fiftration under reduced pressure. Theabove slurrying procedure was repeated twice more but the final time theslurry was diluted to 1,000 ml with water and 2N NaOH was added untilthe solid dissolved. A solid was collected by filtration under reducedpressure and dried overnight in an oven at 60° C. to give the titlecompound (17.2 g).

EXAMPLE 17

This compound was prepared as described for Example 15 (i) except thatthe equivalent molar amount of aniline was used in place of theo-anisidine.

5-Aminoisophthalic acid (36.2 g) was dissolved in water (1 l) withstirring and the pH was adjusted to 8.0 with NaOH solution, then sodiumnitrite (14 g) was added. The resulting solution was poured onto amixture of concentrated HCl (60 cm³) in ice (100 g) at a temperature ofbetween 0 to 10° C. and stirred for 2 hours also at 0 to 10° C. Excessnitrite was removed with a 10% solution of sulphamic adid.

The compound (50 g) from i) above was dissolved in water (400 cm³). Thissolution was poured into the above prepared diazo suspension at atemperature of between 0 to10° C. The reaction, mixture was stirredovernight at pH 7 whilst being warmed slowly to room temperature. Thenthe pH was adjusted 6.0 with concentrated HCl. and 20% w/v NaCl wasadded. The mixture was slowly filtered under reduced pressure to give apaste which was used directly in the next step.

The paste from i) above was stirred in water (2 l) with NaOH pellets (80g). The mixture was warmed to 70 to 80° C. for 3 hours until TLC showedthat the reaction was complete. The mixture was cooled to roomtemperature and 20% w/v NaCl was added. The pH of the mixture was slowlyadjusted to 4.0 with concentrated HCl to form a precipitate which wascollected by filtration under reduced pressure and dried overnight in anoven at 60° C. to give 220.4 g of product.

Metanilic acid (13.2 g) was stirred in water (100 cm³) with stirring andthe pH was adjusted to 7.0 to dissolve the acid. Sodium nitrite solution(37.5 ml, 2N) was added. The resulting solution was poured onto amixture of concentrated HCI (37.5 cm³) in ice (50 g) at a temperature ofbetween 0 to10° C. and stirred for 2 hours also at 0 to 10° C. Excessnitrite was removed with a 10% solution of sulphamic acid.

m-Anisidine was stirred in methanol (50 cm³) and this solution waspoured into the above prepared diazo suspension. The reaction mixturewas stirred overnight whilst being allowed to slowly warm to roomtemperature, and then was filtered and washed with a little saturatedbrine. A solid was collected by filtration under reduced pressure anddried overnight in an oven at 60° C. to give 40.7 g of product.

v) The compound (15.3 g) from iii) above was added to water (300 cm³) atpH 8. The resulting solution was added slowly to a stirred suspension ofcyanuric chloride (3.7 g) in acetone (50 cm³). The mixture was thenpoured onto a mixture of ice and water (100 g) at 0 to 10° C. and at pH6 to 7 and stirred for 2 hours also at 0 to 10° C. and pH 6 to 7 untilTLC showed that the reaction was complete.

The compound (6.1 g) from iv) above was added and the reaction mixturewas warmed 30° C. and stirred at pH 7 overnight.

1-(2-Aminoethyl)piperazine (15.8 g) was added and the mixture was thenwarmed to 75±5° C. for 6 hours and then was cooled to room temperature.

The mixture was acidified to pH 4.0 with concentrated HCl to form aprecipitate which was collected from the reaction mixture by filtrationunder reduced pressure. The solid product was purified as described inthe last paragraph of Example 14 iii) above, to give the title compound(7.9 g).

EXAMPLE 18

The compound (15.3 g) from ex. 17 iii) above was added to water (300cm³) at pH 8. The resulting solution was added slowly to a stirredsuspension of cyanuric chloride (3.7 g) in acetone (50 cm³). The mixturewas then poured onto a mixture of ice and water (100 g) at 0 to 10° C.and at pH 6 to 7 and stirred for 2 hours also at 0 to10° C. and pH 6 to7 until TLC showed that the reaction was complete.

The compound (9 g) from ex. 4 i) above was added and the reactionmixture was warmed to 30° C. and stirred at pH 7 overnight.

1-(2-Aminoethyl)piperazine (15.8 g) was added and the mixture was warmedto 75±5° C. for 6 hours and then was cooled to room temperature.

The mixture was acidified to pH 4.0 with concentrated HCI to form aprecipitate which was collected from the reaction mixture by filtrationunder reduced pressure. The solid product was purified as described inthe last paragraph of Example 14 iii) above, to give the title compound(13.4 g).

EXAMPLE 19

The compound (14.2 g) prepared as described in Example 14 i) above, wasdissolved in water (300 cm³) the pH of which was adjusted to 8.0 withNaOH. The resulting solution was added over 15 minutes to a solution ofcyanuric chloride (4.6 g) in acetone (50 cm³). The mixture was thenpoured onto ice (100 g) and stirred at 0 to 10° C. for 2 hours at pH 6until TLC showed that the reaction was complete.

1-(2-Aminoethyl)piperazine [3.2 g ] was added to the reaction mixturewhich was then stirred at room temperature and pH 9 overnight.

Ethanolamine (9.2 g, 6M) was added and the mixture was warmed to 70±5°C. for 6 hours and then was cooled to room temperature.

The mixture was acidified to pH 4.0 with concentrated HCl to form aprecipitate which was collected from the reaction mixture by filtrationunder reduced pressure. The solid product was purified as described inthe last paragraph of Example 14 iii) above, to give the title compound(14.3 g).

Salts

The exemplified compounds 1 to 19, prepared as described above, wereconverted to their purified ammonium salts as follows. Each example wasstirred in ammonia solution and a solid was collected by filtration. Thecrude ammonium salt thus obtained was then re-dissolved in ammoniasolution the pH of which was adjusted to 9. The solution was dialyseduntil its conductivity was measured to be less than 100 μScm⁻¹. Thesolution was then evaporated to dryness or filtered through Whatman GF/Cand 0.45 μm filter papers to obtain a purified ammonium salt suitablefor use directly in an ink as described below.

Inks

The effectiveness in ink jet printing of compounds of Formula (1) wasdemonstrated as follows. Inks separately comprising each exemplified dyewere prepared by dissolving 2 parts of the ammonium salt, prepared asdescribed above, in 98 parts of a mixture of water and 2-pyrrolidone (ina respective ratio of 90:10 by volume). The inks were printed onto plainpaper using a thermal ink-jet printer to give a bright yellow printwhich had good optical density and light fastness.]

Further inks comprising the exemplified dyes may be may be prepared asdescribed in the following tables in which the number in the firstcolumn (headed Ex. no.) denotes the example number of dye to be used inthe ink. The dye may be in its free acid form andlor in the form of anysuitable salt (e.g. ammonium salt). Numbers quoted in the second columnonwards refer to the number of parts of the relevant ingredient and allparts are by weight. The inks may be applied to paper by thermal orpiezo ink jet printing.

The following abbreviations are used in the tables:

PG = propylene glycol; DEG = diethylene glycol; NMP = N-methylpyrollidone; DMK = dimethylketone; NaST = Na stearate IPA = isopropanol;MEOH = methanol; 2P = 2-pyrollidone; MIBK = methylisobutyl ketone; CET =cetyl ammonium bromide; TBT = tertiary butanol; TDG = thiodiglycol; BDL= butane-2,3-diol; PHO = Na₂HPO₄; and P12 = propane-1,2-diol.

TABLE I Ex. no. Dye Water PG DEG NMP DMK NaOH Na ST IPA MEOH 2P MIBK 12.0 80 5 6 4 5 2 3.0 90 5 5 0.2 3 10.0 85 3 3 3 5 1 4 2.1 91 8 1 5 3.186 5 0.2 4 5 6 1.1 81 9 0.5 0.5 9 7 2.5 60 4 15 3 3 6 10 5 4 8 5 65 5 2010 9 2.4 75 3 4 5 6 5 10 4.1 80 5 2 10 0.3 11 3.2 65 5 4 6 5 4 6 5 125.1 96 4 13 10.8 90 5 5 14 10.0 80 2 6 2 5 1 4 15 1.8 80 5 15 16 2.6 8411 5 17 3.3 80 2 10 2 6 18 12.0 90 7 0.3 3 19 5.4 69 2 20 2 1 3 3

TABLE II Ex. no. Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P P12 1 3.080 15 0.2 5 2 9.0 90 5 1.2 5 3 1.5 85 5 5 0.15 5.0 0.2 4 2.5 90 8 4 0.125 3.1 82 4 8 0.3 6 6 0.9 85 10 5 0.2 7 9.0 90 5 5 0.3 8 4.0 70 10 4 1 411 9 2.2 75 4 10 3 2 6 10 10.0 91 6 3 11 9.0 76 9 7 3.0 0.95 5 12 5.0 785 11 6 13 5.4 86 5 7 7 14 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5 15 2.0 90 1016 2.0 88 10 17 5.0 78 5 12 5 18 8.0 70 2 8 15 5 19 10.0 80 8 12

What is claimed is:
 1. At least one compound of Formula (1):

where n represents from 1 to 5 inclusive; R¹, R^(1B), R⁴ and R^(4B) each independently is H or one of the following substituents, optionally substituted: C₁₋₈alkyl; C₁₋₈alkoxy; —NHCOH, C₁₋₈alkylcarbonylamino; and —NHCONR⁵R⁶ where R⁵ and R⁶ each independently is H, C₁₋₈alkyl and aryl; and R² and R³ each independently is H or one of the following sustituents, optionally substituted: C₁₋₈alkoxy; —NHC₁₋₈alkyleneOH, —SC₁₋₈—alkyleneSO₃H; —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂;

where X comprises one of the following: —NHC₁₋₈alkylene; —NHphenylSO₂NHC₁₋₈alkylene; and a direct link,

where X comprises one of the following: —NHC₁₋₈alkylene; —NHphenylSO₂NHC₁₋₈alkylene; a direct link; and a moiety of Formula (2):

where m and p is each independently from 0 to 5 inclusive, provided that (m+p) is from 1 to 5 inclusive; and R^(1A), R^(2A), R^(4A) and R^(4C) each independently is one of those optionally substituted substituents as defined herein for R¹, R², R⁴ and R^(4B) respectively; a labile atom or group selected from the aroup consisting of halo, a sulphonic acid group, a thiocyano group, an optionally substituted quaternary ammonium group, and an optionally substituted pyridinium group; or a non-labile group selected from the group consisting of —OR⁷, —SR⁸ and —NR⁹R¹⁰; R⁷, R⁸, R⁹ and R¹⁰ are each independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, aralkyl, and R⁹ and R¹⁰ together with the nitrogen atom to which they are attached from an optionally substituted 5- or 6-membered ring; where the optimal substituents herein comprise: C₁₋₄alkyl, C₁₋₄haloalkyl, C₁₋₄haloakoxy, C₁₋₄alkoxy, carboxy, sulpho, hydroxy, amino, mercapto, cyano, nitro and halo; with the proviso that when one of R² and R³ is a moiety of the Formula (2), then the other of R² or R³ is:

a moiety of Formula (2), or —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂; wherein: X¹ is —NHC₁₋₈alkylene or —NHphenylSO₂NHC₁₋₈alkylene.
 2. A compound according to claim 1 wherein: R² and R³ each independently is H or one of the following substituents, optionally substituted: C₁₋₈alkoxy; —NHC₁₋₈alkyleneOH, —S₁₋₈-alkyleneSO₃H; —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂;

where X comprises one of the following: —NHC₁₋₈alkylene, —NHphenylSO₂NHC₁₋₈alkylene; and a direct link; a labile atom or group selected from the group consisting of halo, a sulphonic acid group, a thiocyano group, a quaternary ammonium group, and an optionally substituted pyridinium group; or a non-labile group selected from the group consisting of —OH, —NH₂, —NH(C₁₋₄-alkyl) and -NH(hydroxy C₂₋₄alkyl); where the optional substituents are as defined in claim
 1. 3. A compound of Formula (1) as claimed in claim 1, in which: n is 2; R¹⁸ and R^(4B) represent H; R¹ represents H, C₁₋₈alkyl; C₁₋₈alkoxy; —NHCOH, C₁₋₈alkylcarbonylamino; or -NHCONR⁵R⁶; R⁴ represents H, C₁₋₈alkyl or C₁₋₈alkoxy; and R² and R³ each independently represents: H; C₁₋₈alkoxy; -NHC₁₋₈alkyleneOH, —SC₁₋₈alkyleneSO₃H; —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂,

where X is —NHC₁₋₈alkylene; or a direct link,

where X is —NHC₁₋₈alkylene; or a direct link; or a moiety of Formula(2) where m is 2, p is 0 and R^(4C) represents H; with the proviso that when one of R² and R³ is a moiety of the Formula (2) where m is 2, p is 0 and R^(4C) represents H, then the other of R² and R³ is:

-SC₁₋₈-alkyleneSO₃H, —NHC₁₋₈alkyleneN(C₁₋₈alkyl)₂ or a moiety of Formula (2) where m is 2, p is 0 and R^(4C) represents H; wherein X¹ is —NHC₁₋₈alkylene.
 4. A mono azo dye of Formula (1) as claimed in claim 3, in which: n is 2; R^(1B), R⁴ and R^(4B) are all H; R¹ is H, C₁₋₄alkyl, C₁₋₄alkoxy, NHCOH, C₁₋₄alkylcarbonylamino, or —NHCONR⁵R⁶; where R⁵ and R⁶ is each independently: H, C₁₋₄alkyl or aryl; and R² and R³ is each independently: —NHC₁₋₄alkyleneOH, —SC₁₋₄alkyleneSO₃H, —NHC₁₋₄alkyleneN(C₁₋₄alkyl)₂; or

where X is —NHC₁₋₄alkylene or a direct link.
 5. A bisazo dye of Formula (1) as claimed in claim 3, in which: n is 2; R^(1B) and R^(4B) are both H; R¹ and R^(1A) is each independently: H, C₁₋₄alkoxy, NHCOH, C₁₋₄alkyicarbonylamino, or NHCONR⁵R⁶; where R⁵ and R⁶ is each independently H, C₁₋₄alkyl or aryl; R⁴ and R^(4A) is each independently H, C_(1-4 alkyl or -C) ₁₋₄alkoxy; R² is a moiety of Formula (2) where m is 2, p is 0 and R^(4C) is H; R^(2A) is H, or C₁₋₄alkoxy; and R³ is: -SC₁₋₄alkyleneSO₃H, -NHC₁₋₄alkyleneN(C₁₋₄-alkyl)₂; or

where X is —NHC₁₋₄alkylene.
 6. A monoazo dye of Formula 1, as claimed in claim 3, in which: n is 2; R^(1B), R⁴ and R^(4B) are all H; R¹ is H, C₁₋₄alkyl, C₁₋₄alkoxy, NHCOH, C₁₋₄alkylcarbonylamino, or NHCONR⁵R⁶ where R⁵ and R⁶ is each independently H, C₁₋₄alkyl or aryl; and R² and R³ is each independently: —NHC₁₋₄alkyleneOH, —SC₁₋₄alkyleneSO₃H, —NHC₁₋₄alkyleneN(C₁₋₄-alkyl)₂

where X is —NHC₁₋₄alkylene or a direct link; or

where X is —NHC₁₋₄alkylene or a direct link;

provided that at least one of R² and R³ is
 7. A bisazo dye of Formula 1, as claimed in claim 3, in which: n is 2; R^(1B) and R^(4B) are both H; R¹ and R^(1A) is each independently: H, C₁₋₄alkyl, C₁₋₄alkoxy; —NHCOH, C₁₋₄alkylcarbonylamino or NHCONR⁵R⁶ where R⁵ and R⁶ is each independently H, C₁₋₄-alkyl or aryl; R⁴ and R^(4A) is each independently H, C₁₋₄alkyl or C₁₋₄alkoxy; R² is a moiety of Formula (2) where m is 2; p is 0 and R^(4C) is H; R^(2A) is H; and R³ is

where X is —NHC₁₋₄alkylene.
 8. An ink comprising at least one compound of Formula (1) as claimed in claim 1, 2, or 3, and a suitable medium.
 9. A process for printing a substrate with an ink as claimed in claim 8, in which the ink is applied by ink let printing.
 10. A substrate printed with an ink as claimed in claim 8, the substrate selected from the group consisting of one or more of: paper, an overhead projector slide and a textile material.
 11. A process for the colouring a textile material with an ink as claimed in claim 8, the process comprising the steps of: i) applying the ink to the textile material by inkjet printing; and ii) heating the textile material at a temperature from 50° C. to 250° C. to fix the dye on the material.
 12. A textile material coloured with an ink as claimed in claim
 8. 13. A process for preparing a mono azo compound of Formula (1) as claimed in 1, 3, 4, or 6, in which R³ is other than a moiety of Formula (2), the process comprising condensing a compound of Formula (3);

with at least one compound selected from the group consisting of those of Formulae R²H and R³H.
 14. A process for preparing a bisazo compound of Formula (1) as claimed in any of claims 1, 3, 5 or 7, in which R2 is a moiety of Formula (2), the process comprising condensing a compound of Formula (¹) in which R³ is Cl with a compound of Formula R³H where R³ is other than Cl. 